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Title: Mechanistic study of dry reforming of ethane by CO 2 on a bimetallic PtNi(111) model surface

Here, we report that ethane (CH 3CH 3), one of the primary components of shale gas, is an attractive candidate for the production of syngas (CO + H 2) and ethylene (CH 2CH 2) via the selective C–C and C–H bond cleavage, respectively. Understanding the origin of the selective conversion is essential to the design of a good catalyst for CH 3CH 3 activation. Herein, we combined density functional theory (DFT) calculations with kinetic Monte Carlo (KMC) simulations to shed light on the mechanism of the oxidative C–H and C–C bond cleavage of CH 3CH 3 on a PtNi(111) model catalyst using CO 2 as an oxidant, where the estimated selectivity is in good agreement with the experimental results on PtNi nanoparticles supported on CeO 2. Our calculations show that PtNi is selective to CO via direct CO 2 dissociation and the oxidative C–C bond scission of CH 3CH 3 via the oxygenated (*C 2H yO) intermediates. By comparison the CH 2CH 2 selectivity via the selective C–H bond scission of *CH 3CH 3 is much lower. Lastly, the kinetic analysis suggests that the selectivity of PtNi toward syngas can be enhanced by facilitating the formation of key *C 2Hmore » yO intermediates, while the selectivity toward CH 2CH 2 is promoted mainly by accelerating the C–H bond scission of *CH 3CH 2 to produce *CH 2CH 2.« less
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division; Columbia Univ., New York, NY (United States). Department of Chemical Engineering
Publication Date:
Report Number(s):
BNL-209424-2018-JAAM
Journal ID: ISSN 2044-4753; CSTAGD
Grant/Contract Number:
SC0012704; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 8; Journal Issue: 15; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1481402
Alternate Identifier(s):
OSTI ID: 1454333

Kattel, Shyam, Chen, Jingguang G., and Liu, Ping. Mechanistic study of dry reforming of ethane by CO2 on a bimetallic PtNi(111) model surface. United States: N. p., Web. doi:10.1039/C8CY00880A.
Kattel, Shyam, Chen, Jingguang G., & Liu, Ping. Mechanistic study of dry reforming of ethane by CO2 on a bimetallic PtNi(111) model surface. United States. doi:10.1039/C8CY00880A.
Kattel, Shyam, Chen, Jingguang G., and Liu, Ping. 2018. "Mechanistic study of dry reforming of ethane by CO2 on a bimetallic PtNi(111) model surface". United States. doi:10.1039/C8CY00880A.
@article{osti_1481402,
title = {Mechanistic study of dry reforming of ethane by CO2 on a bimetallic PtNi(111) model surface},
author = {Kattel, Shyam and Chen, Jingguang G. and Liu, Ping},
abstractNote = {Here, we report that ethane (CH3CH3), one of the primary components of shale gas, is an attractive candidate for the production of syngas (CO + H2) and ethylene (CH2CH2) via the selective C–C and C–H bond cleavage, respectively. Understanding the origin of the selective conversion is essential to the design of a good catalyst for CH3CH3 activation. Herein, we combined density functional theory (DFT) calculations with kinetic Monte Carlo (KMC) simulations to shed light on the mechanism of the oxidative C–H and C–C bond cleavage of CH3CH3 on a PtNi(111) model catalyst using CO2 as an oxidant, where the estimated selectivity is in good agreement with the experimental results on PtNi nanoparticles supported on CeO2. Our calculations show that PtNi is selective to CO via direct CO2 dissociation and the oxidative C–C bond scission of CH3CH3 via the oxygenated (*C2HyO) intermediates. By comparison the CH2CH2 selectivity via the selective C–H bond scission of *CH3CH3 is much lower. Lastly, the kinetic analysis suggests that the selectivity of PtNi toward syngas can be enhanced by facilitating the formation of key *C2HyO intermediates, while the selectivity toward CH2CH2 is promoted mainly by accelerating the C–H bond scission of *CH3CH2 to produce *CH2CH2.},
doi = {10.1039/C8CY00880A},
journal = {Catalysis Science and Technology},
number = 15,
volume = 8,
place = {United States},
year = {2018},
month = {6}
}

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